Mechanistically guided one pot synthesis of phosphine-phosphite and its implication in asymmetric hydrogenation

TitleMechanistically guided one pot synthesis of phosphine-phosphite and its implication in asymmetric hydrogenation
Publication TypeJournal Article
Year of Publication2022
AuthorsSen, A, Kumar, R, Pandey, S, K. Raj, V, Kumar, P, Vanka, K, Chikkali, SH
JournalEuropean Journal of Organic Chemistry
Volume2022
Issue2
Paginatione202101447
Date PublishedJAN
Type of ArticleArticle
ISSN1434-193X
Keywordsasymmetric hydrogenation, catalysis, DOPA synthesis, One pot synthesis, Phosphine-phosphite ligand
Abstract

Although hybrid bidentate ligands are known to yield highly enantioselective products in asymmetric hydrogenation (AH), synthesis of these ligands is an arduous process. Herein, a one pot, atom-economic synthesis of a hybrid phosphine-phosphite (L1) is reported. After understanding the reactivity difference between an 0-nucleophile versus C-nucleophile, one pot synthesis of Senphos (L1) was achieved (72%). When L1 was treated with [Rh], P-31 NMR revealed bidentate coordination to Rh. Senphos, in the presence of rhodium, catalyzes the AH of Methyl-2-acetamido-3-phenylacrylate and discloses an unprecedented turn over frequency of 2289, along with excellent enantio-selectivity (92%). The generality is demonstrated by hydrogenating an array of alkenes. The AH operates under mild conditions of 1-2 bar H-2 pressure, at room temperature. The practical relevance of Ll is demonstrated by scaling-up the reaction to 1 g and by synthesizing DOPA, a drug widely employed for the treatment of Parkinson's disease. Computational insights indicate that the R isomer is preferred by 3.8 kcal/mol over the S isomer.

DOI10.1002/ejoc.202101447
Type of Journal (Indian or Foreign)

Foreign

Impact Factor (IF)

3.021

Divison category: 
Physical and Materials Chemistry
Polymer Science & Engineering

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